Cationic triphendioxazine dyes, methods for their manufacture and their use for dyeing cellulosic substrates

ABSTRACT

A dyestuff of formula:   &lt;IMAGE&gt; (I)  wherein: the groups X1 and X2 are independently hydrogen, halogen, alkyl, aryl, alkoxy, cyano, optionally substituted amino or carboxylic acid ester groups; (R)n represents n substituents R each of which is independently halogen, lower alkyl, lower alkoxy or -COOH and n is 0 or 1; R1 is hydrogen, or optionally substituted lower alkyl; Y is an optionally substituted aliphatic or optionally substituted araliphatic group; R2 is hydrogen, optionally substituted lower alkyl, optionally substituted aryl or optionally substituted aralkyl; R3 is hydrogen or an optionally substituted alkyl or aralkyl group; A- is an anion; a is 0 or 1; and Z is hydrogen, optionally substituted lower alkyl, optionally substituted aryl or optionally substituted aralkyl. The dyes are useful for the coloration of materials such as textiles, leather, inks and lacquers.

This invention relates to triphendioxazine dyes, to methods for theirmanufacture and to their use for dyeing cellulosic substrates.

According to the present invention there is provided a dyestuff offormula: ##STR2## wherein:

the groups X₁ and X₂ are independently hydrogen, halogen, alkyl, aryl,alkoxy, cyano, optionally substituted amino or carboxylic acid estergroups;

(R)_(n) represents n substituents R each of which is independentlyhalogen, lower alkyl, lower alkoxy or --COOH and n is 0 or 1;

R₁ is hydrogen, or optionally substituted lower alkyl;

Y is an optionally substituted aliphatic or optionally substitutedaraliphatic group;

R₂ is hydrogen, optionally substituted lower alkyl, optionallysubstituted aryl or optionally substituted aralkyl;

R₃ is hydrogen or an optionally substituted alkyl or aralkyl group;

A⁻ is an anion;

a is 0 or 1; and

Z is hydrogen, optionally substituted lower alkyl, optionallysubstituted aryl or optionally substituted aralkyl.

The term "lower alkyl" as used herein means an alkyl group having from 1to 6 carbon atoms. In general, lower alkyl groups having from 1 to 4carbon atoms are preferred.

The groups X₁ and X₂ are both preferably halide, for example chloride.

In the groups (R)_(n), n is preferably 0 or when n is 1, the groups Rare preferably the same and R is preferably a halide group, especiallychloride.

R₁ is preferably hydrogen or methyl.

As examples of groups represented by Y there may be mentioned ethylene,1,2- and 1,3-propylene, 2-hydroxy-1,3- propylene, 1- and2-phenyl-1,3-propylene, 2-(4'-sulphophenyl)- 1,3-propylene, 1,4-, 2,3-and 2,4-butylene, 2-methyl-1,3-propylene, 2-methyl-2,4-pentylene,2,2-dimethyl-1,3-propylene, 1-phenylethylene, 1-chloro-2,3-propylene,1,6- and 2,5-hexylene, 2,3-diphenyl-1,4-butylene,1(methoxycarbonyl)-1,5-pentylene, 1-carboxy-1,5-pentylene,2,7-heptylene, 3-methyl-1,6-hexylene, --CH₂ CH₂ OCH₂ CH₂ --, --CH₂ CH₂SCH₂ CH₂ --, --CH₂ CH₂ SSCH₂ CH₂ --, ##STR3##

R₁ be linked to both nitrogen atoms in the structure: --NR₁ --Y--NR₂ --.As examples of such a grouping there may be mentioned ##STR4##

Y is preferably a linear or branched chain aliphatic group containingfrom 2 to 6 carbon atoms and optionally containing one or more hydroxyor alkoxy substituents, for example an ethylene or propylene groupoptionally containing one hydroxy or methoxy substituent.

As examples of atoms or groups represented by R₂ there may be mentionedhydrogen, methyl, hydroxymethyl, ethyl, hydroxyethyl, phenyl, 3- and4-nitrophenyl, benzyl, beta-hydroxyethyl and beta-sulphatoethyl.

The dyestuffs of the present invention are conveniently prepared byde-sulphonation of the compound: ##STR5## Compound (II) may be preparedas described for example in United Kingdom Patent Specification No.1450746 by reacting 2,3,5,6-tetrachloro-1,4-benzoquinone (or thecorresponding compound bearing the substituents X₁ and X₂ where theseare not chlorine atoms) with 2 moles of a diamine of formula: ##STR6##and heating the resulting dianilide in the presence of a strongly acidcondensing agent such as oleum to effect ring closure. De-sulphonationof compound (II) may be achieved by heating in the presence of a mineralacid, for example sulphuric acid, and preferably in the presence ofsulphuric acid having a concentration in excess of 80% by weight.Suitable reaction temperatures are in the range of about 90° C. to 150°C.

Conversion of the dyestuff to the salt or quaternary derivative may beachieved, either before or after de-sulphonation, by conventional means,for example by treatment with the appropriate dialkyl sulphate or alkyliodide. If groups such as R₂ and Z are hydrogen, these may be convertedto alkyl on treatment with the alkylating agent.

Z and R₂ are preferably independently hydrogen, a lower alkyl group or alower alkyl group having a hydroxyl substituent. We have found thatimproved solubility in aqueous acids may be obtained when Z and R₂ areindependently lower alkyl groups, for example methyl or ethyl, and suchcompounds are especially preferred. R₃, when present, is preferablyhydrogen or a lower alkyl group. When a is 1 and R₃ is hydrogen, thedyestuff is the corresponding salt, and when a is 1 and R₃ is a loweralkyl group, the dyestuff is the corresponding quaternary derivative.The nature of the anion A⁻ is not critical.

The new dyestuffs are basic triphendioxazine dyes of blue shades usefulfor the colouration of materials such as textiles, leather, inks andlacquers. The basic triphendioxazine dyestuffs have an especially highaffinity for paper and backwaters from paper dyeing are frequentlysubstantially clear. The basic triphendioxazine dyestuffs have hightinctorial strengths and good light fastness on cellulosic substrates.

The invention is illustrated by the following Examples in which allparts and percentages are by weight unless otherwise stated.

EXAMPLE 1

A mixture of 5 parts of6,13-dichloro-3,10-bis-(2-aminoethylamino)triphendioxazine-4,11-disulphonicacid (formula III below wherein Y is --CH₂ CH₂ -- and R₂ and Z arehydrogen) and 30 parts of 98% sulphuric acid was stirred at 130° C. for1 hour. ##STR7## The mixture was cooled to 25° C., poured onto 400 partsof ice/water and neutralised to pH 7.0 with sodium hydroxide solution.The precipitated product was filtered off, washed with water to removeany sodium sulphate and dried.

Analysis showed the product to be6,13-dichloro-3,10-bis(2-aminoethylamino)triphendioxazine of formula(IV) below wherein Y is --CH₂ CH₂ -- and R₂ and Z are hydrogen. The massspectrum showed a terminal ion at m/e=470 and a breakdown patternconsistent with this structure. The product dissolved in aqueous aceticacid to give a blue solution having lambda max 568 mm which dyed paperand polyacrylonitrile textile materials in reddish-blue shades. Theproduct could also be applied to aromatic polyester textile materials,at pH 7.0. ##STR8##

EXAMPLE 2

The process of Example 1 was repeated except that the starting materialhad the formula of compound (III) above wherein Z and R₂ are both methyland Y has the formula: --CH₂ CH₂ CH₂ --.

The resultant product was a dyestuff of formula (IV) wherein Y, R₂ and Zhave the meanings given above. The product had a lambda (max) value of570 mm and dyed paper and polyacrylonitrile materials in reddish-blueshades.

EXAMPLE 3

The process of Example 1 was repeated except that the starting materialhad the formula of compound (III) above wherein Z is hydrogen, R₂ is--CH₂ CH₂ OH and Y has the formula: --CH₂ CH₂ --. The resultant productwas a dyestuff of formula (IV) wherein Y, R₂ and Z have the meaningsgiven above. The product had a lambda (max) value of 560mm and dyedpaper and polyacrylonitrile materials in reddish-blue shades.

EXAMPLE 4

The process of Example 1 was repeated except that the starting materialhad the formula of compound (III) above wherein Z and R₂ are bothhydrogen and Y has the formula: --CH₂ CH₂ CH₂ --. The resultant productwas a dyestuff of formula (IV) wherein Y, R₂ and Z have the meaningsgiven above. The product had a lambda (max) value of 560 mm and dyedpaper and polyacrylonitrile materials in reddish-blue shades.

EXAMPLE 5

25 parts of the starting material of Example 1 was stirred with 600parts of water at 35 ° to 40° C. and the pH was adjusted to 10.5. 12Parts of dimethyl sulphate was added and the mixture was stirred at pH10.5 for 11/2 hours. The pH was adjusted to 8 and the solid was isolatedby filtration, washed with water and dried to give 16 parts of a darkblue solid.

A mixture of the above solid and 80 parts of concentrated sulphuric acidwas stirred at 130° C. for 1 hour. On cooling to 25° C., the mixture waspoured into 1600 parts of ice/water and the pH was adjusted to 7.0 withsodium hydroxide. Salt was added to precipitate the product which wasisolated by filtration to give 10 parts of cationic dyestuff whosestructure was that of formula I wherein X₁ and X₂ are both chlorine, R₁is hydrogen, R₂, R₃ and Z are all methyl, n is 0, Y is --CH₂ CH₂ --, ais 1 and A⁻ is Cl⁻.

The product dissolved in water to give a blue solution having a lambdamax value of 565 mm which dyed paper and polyacrylonitrile materials inreddish-blue shades.

EXAMPLES 6 to 13

Dyes of formula (I) which may be prepared using the method of Example 1when a is 0 and the method of Example 6 when a is 1 are listed inTable 1. Approximate values for lambda max are given for each dye.

                                      TABLE I                                     __________________________________________________________________________    Substituent in                                                                       EXAMPLE No.                                                            Formula I                                                                            6         7   8      9   10  11  12  13                                __________________________________________________________________________    R      --        --  --     --  --  Cl  Cl  Cl                                n      0         0   0      0   0   1   1   1                                 R.sub.1                                                                              H         H   H      H   H   H   H   CH.sub.3                          Y      --CH.sub.2 CHOHCH.sub.2 --                                                              (CH.sub.2).sub.2                                                                  (CH.sub.2).sub.2                                                                     (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.2                                                                  (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.2                  R.sub.2                                                                              H         H   CH.sub.2 CH.sub.2 OH                                                                 C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          H   CH.sub.3                                                                          CH.sub.3                          R.sub.3                                                                              --        --  --     --  --  --  --  CH.sub.3                          Z      H         H   H      C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          H   CH.sub.3                                                                          CH.sub.3                          a      0         0   0      0   0   0   0   1                                 A.sup.-                                                                              --        --  --     --  --  --  --  Cl                                X.sub.1                                                                              Cl        Br  Br     Cl  Br  Cl  Cl  Cl                                X.sub. 2                                                                             Cl        Br  Br     Cl  Br  Cl  Cl  Cl                                λmax (nm)                                                                     --        562 558    571 566 564 568 552                               __________________________________________________________________________

We claim:
 1. A triphendioxazine dyestuff of blue shade having theformula: ##STR9## wherein X₁ and X₂ are both halogen;(R)_(n) representsn substituents R each of which is independently halogen and n is 0 or 1;R₁ is hydrogen or a lower alkyl group; Y is a linear or branchedaliphatic group containing from 2 to 6 carbon atoms and optionallycontaining one or more hydroxy or alkoxy substituents; R₂ is hydrogen,lower alkyl, hydroxy substituted lower alkyl, phenyl, 3- or 4-nitrophenyl, benzyl or beta-sulphatoethyl; R₃ is hydrogen or a loweralkyl group; A⁻ is an anion and a is 1 or 0; and Z is hydrogen or alower alkyl group.
 2. A dyestuff according to claim 1 wherein X₁ and X₂are both chlorine; n is 0; R₁ is hydrogen or methyl, Y is a linear orbranched aliphatic group containing from 2 to 6 carbon atoms; R₂ ishydrogen, lower alkyl or hydroxy substituted lower alkyl; R₃ is hydrogenor lower alkyl, A⁻ is an anion and a is 1 or 0; and Z is hydrogen or alower alkyl group.
 3. A dyestuff according to claim 1 wherein X₁ and X₂are both chlorine; n is 0; R₁ is hydrogen; R₂ is hydrogen or loweralkyl; Y is ethyl or propyl; a is 0; and Z is hydrogen or a lower alkylgroup.
 4. A dyestuff according to claim 3 wherein R₂ and Z are bothlower alkyl.
 5. A dyestuff according to claim 4 wherein R₂ and Z areboth methyl.
 6. A dyestuff according to claim 1 wherein X₁ and X₂ areboth chlorine; n is 0; R₁ is hydrogen or lower alkyl; R₂ is lower alkyl;Y is ethyl or propyl; a is 1; R₃ is lower alkyl and Z is lower alkyl. 7.A process for the manufacture of a dyestuff according to claim 1 whichcomprises de-sulphonation of a compound of formula: ##STR10## by heatingin the presence of a mineral acid.
 8. A process according to claim 7wherein the mineral acid is sulphuric acid having a concentration inexcess of 80% by weight and the reaction temperature is in the range of90 ° to 150° C.
 9. A process for dying cellulosic substrates using adyestuff according to any of claims 1 to 6.